2-aminobenzothiazol phosphates and phosphonates used as insecticides

ABSTRACT

Compounds of the formula IN WHICH R and R1 are hydrogen or halogen, R2 is alkoxy, and R3 is alkoxy or alkyl, are used as insecticides.

United States Patent Fancher 1 Oct. 24, 1972 [54] Z-AMINOBENZOTHIAZOL[56] References Cited PHOSPHATES AND PHOSPHONATES [TED T A USED AsINSECTICIDES 3 520 929 7 /1920 S SI u TENTS 260 30s 72 Inventor:Llewellyn w. Fancher, Orinda,

Calif- Primary Examiner-Albert T. Meyers 73 Assignee: Stauffer ChemicalCompany, New Assistant Brawler-Leonard Schenkman York, Attorney-Damel C.Block et a1.

[22] Filed: Feb. 16, 1971 [57] ABSTRACT PP 115,871 Compounds oftheiformula Related US. Application Data R 2 X TN [62] Division of Ser.No. 837,880, June 30, 1969, I I O Pat. No. 3,597,439. mnemsl R3 R1 S[52] US. Cl. ..424/200 in which R and R1 are h g or halogen R2 is Int.Cl- ..A0ln k y d R3 i alkoxy o lkyl are used as insecticides.

Field of Search ..424/200; 260/305 7 Claims, No Drawings 1 2Z-AMINOBENZOTHIAZOL PHOSPHATFSAND phosphate salt, and dimethyl formamideas a solvent PHOSPHONATES USED AS INSECTICIDES medium which facilitatesand promotes the reaction. This application is a divisional of copendingapplica- Although other solvents such as ketones, alcohols, tion, Ser.No. 837,880, filed June 30, 1969 now US. benzene-H O mixtures, etc., canbe used, DMF has Pat. No. 3,597,439. 5 been found most advantageous withregard to reaction This invention relates to the use of certain noveltimes and yields. It has also been found that a small exchemicalcompounds asinsecticides, more particularly, cess of triethylarnine isadvantageous in bringing the the compounds are certain2-aminobenzothiazole reaction to completion. phosphates andphosphonates. After the completion of the reaction between the Thecompounds of the present invention that are chloroacetarnide and thephosphate, or phosphonate usefulasinsecticides are those having theformula: amine salt, the product is conveniently isolated by pouring themixture into water. Ifthe product is a solid,

R 2 p it is filtered off and recrystallized if desired. If the N productis a liquid, it can be extracted with a solvent H I fi such as benzene,chloroform, etc. 7/ Kg Nn0c1ns 1' R Chloroacetarnide derivatives areused for economic I reasons; however, bromo or iodoacetamides can alsobe used. in which R and R are hydrogen, or halogen, preferablyPreparation of the cPmpounds of this invention is chlorine, R is alkoxyhaving 1 to 5 carbon atoms, and l y the followlng examples- R is alkoxyhaving one to five carbon atoms, I [P preferably 1 to 3 carbon atoms, oralkyl having one to EX LEI five carbon atoms, preferably one to twocarbon atoms. 2-0 Isopropyl, ethylphosphono dithioylacetamide- Thecompounds having the formula: benzothiazole R2 N OH:

0 s (5 b LNEKHJCHQSIIL\R3 N 11-011 1 s I I o s 0 R H Um siNHgcflgs inwhich R, R R and R are as defined above by the m h a 937 m followingreactions:

1? DMF K? 23.9g (0.13M) r 0-isopropyl, ethyl EtflN phosphonodithioicacid 18 diluted with 10 ml. of

R3 R3 dirnethyl forrnamide. The mixture is cooled in an ice R bath andmade slightly basic (below 30 C.) with an- N DMF 40 hydroustriethylamine (about 19 ml.) (0.14M).

1? 0 JL I W The solution is then added to 18.1 g (0.08M) of 2- 3 CICHANchloro-acetamidebenzothiazole dissolved in 50 ml. of

Ra S R! dimethyl-formamide. A moderate temperature rise occurs onmixing. The reaction is completed by stirring at R -60 C. for 2 hours.The liquid product is isolated by N extraction with benzene. The yieldis 23gm. (77 peri J I H cent oftheory), NJ 1.6135.

lNHooHzsP Et N-HCI The following is a Table of certain selected comi S ipounds that are preparable according to the procedure r 50 describedhereto. Compound numbers are assigned to The reaction of a haloacetamidewith a salt of an oreach p n and are used oughout e ganic phosphate toform an acetamido phosphate is remainder he Application. well-known:

TABLE I N or 3 $9? Compound N R R R R c. RNHCCHQX BsP oR umber mp 639 ll1 H H c,H,o c,H,'0 98-l0l BX 2 H H a a 1585.0 .W 3 H H i-C,H-,O c ii1.6135 4 H H c,i-i,0 cm, 1.6292 5 H n i-c,n,o C,H5 1.6015 The samegeneral method is used in the preparation 6 H H CH3) Cam 1,6070

0 e n c O of the compounds of this invention; however, certain 3 5 i2,342 gggig 1339 modifications of the above reaction have been made to 9H E Z Z simplify the procedure and to insure in most instances, it a i cn o 5,3, {08112:

g a z a h gh yields. The modifications include the use of an 12 H CHaOCHs 107410. hydrous triethylamme which obviates the isolation of 13 10 Hi-C,H,0 cm, -84

The following insect species were used in evaluation tests forinsecticidal activity:

1. Housefly (HF) Musca domestica (Linn.)

2. Lygus Bug (LB) Lygus hesperus (knight) 3. Bean Aphid (BA) Aphis fabae(Scop.)

The housefly (HF) was used in evaluation tests of selected compounds asinsecticides by the following procedure. A stock solution containing 100#g/ml. of the toxicant in an appropriate solvent was prepared. Aliquotsof this solution were combined with 1 milliliter of an acetone-peanutoil solution in a glass Petri dish and allowed to dry. The aliquots werethere to achieve desired toxicant concentration ranging from 100 pig/perPetri dish to that at which 50 percent mortality was attained. The Petridishes were placed in a circular cardboard cage, closed on the bottomwith cellophane and covered on top with cloth netting. 25 femalehouseflies, three to five days old, were introduced into the cage andthe percent mortality was recorded after 48 hours. The LD-50 values areexpressed in terms of pg per 25 female flies. The results of thisinsecticidal evaluation test are given in Table II underl-lF. 7

In the Lygus Bug (LB) Lygus hesperus test, ten to 25 two-week old nymphsof Lygus Bug were placed in .separate circular cardboard cages, sealedon one end with cellophane, and covered by a cloth netting on the other.Aliquots of the toxicants, dissolved in an appropriate solvent, werediluted in water containing 0.002 percent of a wetting agent, Sponto 221(a polyoxyether'of alkylated phenols blended with organic sulfonates).Test concentrations ranged from 0.05 per cent downward to that at which50 percent mortality was obtained. Each of the aqueous suspensions ofthe candidate compounds were sprayed onto the insect through the clothnetting by means of a hand-spray gun. Percent mortality in each caserecorded after 24 and 72 hours counts were made to determine living anddead insects. The LD-50 values expressed as percent of toxicant in theaqueous spray were calculated and recorded. These values are reportedunder the column LB in Table II.

The insect species Black Bean Aphid (BA) Aphis fabae (Scop.) was alsoemployed in the test for insecticidal activity. Young nasturtium(Tropaeolum sp.) plants, approximately 2 to 3 inches tall, were used asthe host plants for the bean aphid. The host plant was infested withapproximately 50 75 of the aphids. The test chemical was dissolved inacetone, added to water which contained a small amount of Sponto 221",an emulsifying agent. The solution was applied as a spray to theinfested plants. Concentrations ranged from 0.05 percent downward untilan LD-50 value was achieved. These results are given in Table 11 underthe column BA.

TABLE II (LD VALUES) Compound HF LB BA Number: g

l 30 .05 .03 2 .05 3 .5 .05 .003 4 l0 .05 .00! 5 30 .05 .005 6 100 .05.03 7 I00 .05 .05 8 l2 .05 .05 9 30 .05 .008 10 9 .05 .005 l l 5.5 .05.005 l 2 30 .05 .03 l 3 30 .05 .03 14 30 .05 .008

As those in the art are well aware, various techniques are available forincorporating the active component or toxicant in suitable pesticidalcompositions. Thus, the pesticidal compositions can be convenientlyprepared in the form of liquids or solids, the latter preferably ashomogeneous free-flowing dusts commonly formulated by admixing theactive component with finely divided solids or carriers as exemplifiedby talc, natural clays, diatomaceous earth, various flours such aswalnut shell, wheat, soya bean, cotton-seed and so forth. 7

Liquid compositions are also useful and normally comprise a dispersionof the toxicant in a liquid media, although it may be convenient todissolve the toxicant directly in a solvent such askerosene, fuel oil,xylene, alkylated naphthalenes or the like and use such organicsolutions directly. However, the more common procedure is to employdispersions of the toxicant in an aqueous medium and such compositionsmay be produced by forming a concentrated solution of the toxicant in asuitable organic solvent followed by dispersion in water, usually withthe aid of surface active agents. The latter, which may be anionic,cationic, or nonionic types, are exemplified by sodium stearate,potassium oleate, and other alkaline metal soaps and detergents such assodium lauryl sulfate, sodium napthalene sulfonate, sodium alkylnapthalane sulfonate, methyl cellulose, fatty alcohol ethers, polyglycolfatty acid esters and other polyoxyethylene surface active agents. Theproportion of these agents commonly comprises 1-15 percent by weight ofthe pesticidal compositions although the proportion is not critical andmay be varied to suit any particular situation.

Iclaim:

l. A method of controlling insects comprising applying to the habitatthereof an insecticidally effective amount of a compound of the formula:

in which R and R are hydrogen, or halogen, R is alkoxy having one tofive carbon atoms, and R is alkoxy having one to five carbon atoms, oralkyl having one to five carbon atoms.

2. The method of claim 1 in which R and R are hydrogen, R is alkoxyhaving one to five carbon atoms, and R is alkyl having one to fivecarbon atoms.

3. The method of claim 1 in which R is hydrogen, R is chlorine, R isalkoxy having one to five carbon atoms, and R is alkyl having one tofive carbon atoms.

4. The method of claim 1 in which R is isopropoxy and R is ethyl.

5. The method of claim 1 in which R is ethoxy, and R is ethyl.

6. The method of claim 1 in which R is hydrogen, R 5 is 3-ch1oro, R isisopropoxy and R is ethyl;

7. The method of claim 1 in which R is hydrogen, R is 3-chloro, R isethoxy, and R is ethyl.

2. The method of claim 1 in which R and R1 are hydrogen, R2 is alkoxyhaving one to five carbon atoms, and R3 is alkyl having one to fivecarbon atoms.
 3. The method of claim 1 in which R is hydrogen, R1 ischlorine, R2 is alkoxy having one to five carbon atoms, and R3 is alkylhaving one to five carbon atoms.
 4. The method of claim 1 in which R2 isisopropoxy and R3 is ethyl.
 5. The method of claim 1 in which R2 isethoxy, and R3 is ethyl.
 6. The method of claim 1 in which R ishydrogen, R1 is 3-chloro, R2 is isopropoxy and R3 is ethyl.
 7. Themethod of claim 1 in which R is hydrogen, R1 is 3-chloro, R2 is ethoxy,and R3 is ethyl.